US4064080A - Latex of styrene polymers with terminal amino-sulfonated groups and method of making - Google Patents

Latex of styrene polymers with terminal amino-sulfonated groups and method of making Download PDF

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US4064080A
US4064080A US05713056 US71305676A US4064080A US 4064080 A US4064080 A US 4064080A US 05713056 US05713056 US 05713056 US 71305676 A US71305676 A US 71305676A US 4064080 A US4064080 A US 4064080A
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styrene
weight
monomer
monomers
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US05713056
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Jean-Claude Daniel
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Rhone-Poulenc Industries
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Rhone-Poulenc Industries
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N11/00Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/02Enzymes or microbial cells being immobilised on or in an organic carrier
    • C12N11/08Enzymes or microbial cells being immobilised on or in an organic carrier carrier being a synthetic polymer
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02Monomers containing only one unsaturated aliphatic radical
    • C08F12/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06Hydrocarbons
    • C08F12/08Styrene

Abstract

A dispersion of particles having an average diameter within the range of 0.05 to 3 μm formed of a homo- or copolymer of styrene having terminal ##STR1## groups and a glass transition temperature above 20° C, and the use of such latex for fixing proteins.

Description

The invention relates to styrene polymers which have terminal ##STR2## groups and latices containing same. It is also concerned with a method of preparing said latices.

It has previously been proposed to prepare styrene polymers having terminal ##STR3## groups by mass polymerization of the styrene in the presence of a chain-transfer agent such as aminophenyl disulphide, but the yields are very low and the polymer has to be dissolved and precipitated for purification before it can be obtained in granular form.

Also known are polybutadiene latices having terminal ##STR4## groups, prepared by emulsion polymerization of butadiene in the presence of a chain-transfer agent such as aminophenyl disulphide and an organo-soluble initiator. However, the application of this polymerization method to styrene monomers leads to slow emulsion polymerizations, in which it is often necessary to disperse the chain-transfer agent by means of a solvent, and to secondary mass polymerization of the major part of the styrene monomer, as well as to poor yields and to unstable latices.

The products, prepared in accordance with the practice of this invention, do not suffer from these disadvantages and they form dispersions which are stable under storage and under mechanical shock; the method whereby they are polymerized is simple and does not require the presence of a solvent for introducing the chain-transfer agent; there is no secondary mass polymerization, and yields are good.

According to the invention, the styrene polymers having terminal ##STR5## groups are characterized in that they are in the form of stable latices, the polymer particles of which have an average diameter of between 0.05 and 3 μm, and in that they have a glass transition temperature above 20° C.

The polymer particles having an average diameter of between 0.05 to 3 μm and preferably between 0.1 to 1 μm generally constitute 1 to 70% by weight and preferably 5 to 50% by weight of the latex in accordance with the invention. However, the latex may be diluted without adversely affecting its stability.

The expression "styrene polymer" means the homopolymers of styrene or of styrene derivatives such as methyl styrenes, vinyl toluene, ethyl styrene as well as the copolymers of styrene or its derivatives and copolymerizable vinyl monomers such as alkyl acrylates and alkyl methacrylates, the alkyl group of which contains 1 to 10 atoms of carbon, acrylonitrile and methacrylonitrile, or diene monomers such as butadiene and its derivatives. This comonomer may represent up to 90% by weight of the copolymer and preferably less than 50% by weight thereof, provided that the glass transition temperature is above 20° C.

In the method of the invention, the styrene monomeric component is polymerized either alone or mixed with a copolymerizable vinyl monomer or diene monomer, in an aqueous emulsion in the presence of a chain-transfer agent, such as aminophenyl disulphide or aminophenyl mercaptan, present in an amount within the range of 0.1 to 10% by weight of the monomer, and at least one emulsifying agent and a water-soluble diazo initiator.

The styrene compound may be, among others, styrene and its derivatives such as methyl styrene, vinyl toluene and ethyl styrene.

Examples of the copolymerizable vinyl monomers that may be used are acrylonitrile and methacrylonitrile and alkyl acrylates and alkyl methacrylates, the alkyl group of which contains 1 to 10 carbon atoms, and examples of the diene monomers that may be used are butadiene and its derivatives. The copolymerizable monomer is used in quantities which may be as high as 90% by weight of the monomer mixture, but generally the proportion thereof does not exceed 50% by weight. The proportion is dependent upon the glass transition temperature of the polymer to be obtained, which temperature should be above 20° C. All or part of the monomers is introduced before the commencement of polymerization, and in the latter case the remaining part is introduced in successive fractions or continuously during polymerization. The monomers may likewise be introduced during polymerization, in successive fractions or continuously. The procedure for introducing the monomers will depend upon the required mean size of the latex particles.

The aminophenyl disulphide or aminophenyl mercaptan type transfer agent is represented in particular by o,o'-dithio-bis-aniline, p,p'-dithio-bis-aniline, 2-mercaptoaniline, 3-mercapto-aniline and 4-mercapto-aniline. This agent is generally employed in solution in the monomer or monomers in proportions of between 0.1 and 10% and preferably of between 0.5 and 5% by weight of the monomer or monomers.

The emulsifying agent may be anionic and/or cationic and/or non-ionic of the type conventionally used in emulsion polymerizations. Examples of anionic emulsifying agents that may be used are: the fatty acid salts; the alkaline alkyl sulphates, alkyl sulphonates, alkyl aryl sulphonates, alkyl sulphosuccinates, alkyl phosphates; the alkyl sulphosuccinates; the alkyl-phenol polyglycol ether sulphonates; the alkylsulpho polycarboxylic acid ester salts; the condensation products of fatty acids and oxy- and amino-alkanesulphonic acids; the sulphated derivatives of polyglycol ethers; the sulphated esters of fatty acids and polyglycols; and the alkanol amides of sulphated fatty acids.

Examples of cationic emulsifying agents that may be used are represented by alkylamines and their water-soluble salts, and the soluble salts of alkylamines wherein N is substituted by alkyl and/or alkylaryl and/or hydroxyalkyl radicals. The non-ionic emulsifying agents that may be used are represented by the polyalcohol fatty esters, fatty acid alkanolamides, ethylene polyoxides, ethylene-propylene copolyoxides and oxyethylene alkyl-phenols.

The quantities of emulsifying agent or agents to be used are in the order of 0.05 to 10% by weight of the monomer or monomers, and said agent or agents is or are introduced in totality or in part prior to polymerization, the remaining part being added to the reaction medium during polymerization in successive increments or continuously, depending upon the average diameter desired of the latex particles.

Examples of the water-soluble diazo initiator that may be used are sulphonated azonitriles of the type disclosed in French Pat. No. 1,233,582 and of which the following may be mentioned: azo-bis-(sodium isobutyronitrile sulphonate), azo-bis-(sodium α-methyl-butyronitrile sulphonate), azo-bis-(sodium α-methyl β-ethoxy-carbonylbutyronitrile sulphonate); carboxylic azo-nitriles such as 4,4'-azo-bis-(4-cyanopentanoic) acid and its salts; azo-bis-alkylamidinium salts, such as α,α'-azo-bis-isobutyramidinium chloride and azo-bis-N,N'-dimethylene isobutyramidinium chloride.

The initiator, employed in quantities of 0.01 to 3% and preferably 0.1 to 1% by weight of the monomer or monomers, is introduced in totality or in part prior to polymerization, the remaining part being added to the reaction medium during polymerization, in successive fractions or continuously, particularly when the half-life of the initiator at polymerization temperature is short.

The quantity of water to be used in polymerization should be such that the concentration of the monomer or monomers is between 1 and 70% and preferably between 5 and 50% by weight.

The polymerization temperature, which is a function of the initiator used, is generally between 20° and 100° C and preferably between 40° and 90° C.

The latices in accordance with the invention can be used for fixing proteins on the polymer by covalent chemical bonds. The obtained latices of polymer-protein complex are then used for purifying other proteins or as diagnostic reagents.

Embodiments of the invention are hereinafter given by way of non-limiting examples in which the proportions are expressed as parts by weight.

EXAMPLE 1

The following were introduced into a reaction vessel:

300 parts of softened water,

3.8 parts of cetyltrimethyl ammonium chloride,

100 parts of styrene, and

1 part of p,p'-dithio-bis-aniline.

Air was eliminated by passing a stream of nitrogen through the mixture which was then heated to 50° C with stirring, this temperature being maintained during the entire period of the reaction.

When the mixture had reached a temperature of 50° C, 0.13 part of α,α'-azo-bis-isobutyramidinium chloride was added, and polymerization was allowed to proceed for a period of 22 hours. The mixture was then cooled.

For a conversion rate of 80% by weight, a latex was obtained having a particle concentration of 20% by weight. These particles had an average diameter of 0.1 μm.

After six months, the latex obtained contained no flocculate, which demonstrates its good stability during storage.

A portion of the latex was coagulated, and the polymer obtained was dried and then dissolved in benzene and precipitated with methanol three times. The glass transition temperature Tg was determined on the separated polymer in a Du Pont DSC 990 apparatus fitted with a corundum reference cell, and in an argon atmosphere with a linear temperature rise of 20° C/min. The number of --NH2 functions were also measured by dissolving a known weight of polymer in a mixture of benzene and acetic acid and then titrating the solution with perchloric acid, standardized with potassium acid phthalate; this operation was followed by potentiometry.

The Tg was 82° C.

The polymer contained 2 × 10-5 moles of --NH2 per gram.

EXAMPLE 2

The same prcedure as in Example 1 was employed except that 3.5 parts of sodium laurylsulphate was used instead of the 3.8 parts of cetyltrimethyl ammonium chloride, and 0.2 part of azo-bis-(sodium α-methylbutyronitrile sulphonate) was used instead of the 0.13 of one part of α,α'-azo-bis-isobutyramidinium chloride.

The conversion rate was 90% by weight,

the latex concentration was 23% by weight,

the particle diameter was 0.1 μm,

the latex remained stable after being stored for more than six months, and

the polymer had a Tg of 85° C and contained 2.2 × 10-5 moles of --NH2 per gram.

EXAMPLE 3

The following were introduced into a reaction vessel:

1000 parts of water,

7 parts of dihexyl sulphosuccinate,

100 parts of styrene, and

2.5 parts of p,p'-dithio-bis-aniline.

Air was eliminated by passing a stream of nitrogen through the mixture which was then heated to 70° C while being stirred, which temperature was maintained during the entire period of the reaction.

When the mixture had reached 70° C, 1.1 parts of azo-bis-(sodium, α-methylbutyronitrile sulphonate) was added thereto, and polymerization was allowed to proceed for 22 hours. The mixture was then cooled.

For purposes of comparison, the same procedure was carried out but without p,p'-dithio-bis-aniline.

The following results were obtained:

______________________________________                       Comp.               Example 3                       Example______________________________________conversion rate          % by weight                     80        87latex concentration          % by weight                     7         7.3particle average diameter          μm      0.3       0.2stability of latex          6 months   >         >polymer: Mn*              10 200    188 000 Mw*                      19 000    541 000 Tg            ° C 80        97 quantity of --NH.sub.2          moles/g    10 × 10.sup.-5                               0______________________________________ *Mn = number-average molecular weight *Mw = weight-average molecular weight, determined by gel-permeation chromatography.

The difference between the molecular weights and the Tg of the Example 3 product and the comparative product show that the p,p'-dithio-bis-aniline performed the function of chain-transfer agent in an effective manner and was firmly fixed on the polymer.

Claims (16)

I claim:
1. Styrene polymers having terminal ##STR6## groups in the form of stable latices, the polymer particles of which have an average diameter of between 0.05 and 3 μm and a glass transition temperature above 20° C.
2. Polymers as claimed in claim 1 comprising homopolymers of styrene or its derivatives.
3. Polymers as claimed in claim 1 comprising copolymers of styrene or its derivatives with vinyl monomers.
4. Polymers as claimed in claim 1 comprising copolymers of styrene or its derivatives with diene monomers.
5. A method of preparing latices of polymers having terminal ##STR7## groups, in the form of stable latices, the polymer particles of which have an average diameter of between 0.05 and 3 μm and a glass transition temperature above 20° C, comprising polymerizing a styrene compound, alone or in admixture, with a copolymerizable vinyl monomer in an aqueous emulsion in the presence of 0.1 to 10% by weight of a chain transfer agent, selected from the group consisting of aminophenyl disulphide and aminophenyl mercaptan at least one emulsifying agent, and a water soluble diazo initiator.
6. The method as claimed in claim 5, in which the copolymerizable vinyl monomer is replaced in whole or in part with a copolymerizable diene monomer.
7. A method as claimed in claim 6 in which the diene monomer is selected from the group consisting of butadiene and its derivatives.
8. A method as claimed in claim 5 in which the styrene compound is selected from the group consisting of styrene, methyl styrene, vinyl toluene and ethyl styrene.
9. A method as claimed in claim 5 in which the vinyl monomer is selected from the group consisting of acrylonitrile, methacrylonitrile, alkyl acrylates and alkyl methacrylates in which the alkyl group contains from 1 to 10 carbon atoms.
10. A method as claimed in claim 8 in which the vinyl monomer is present in an amount up to 90% by weight.
11. A method as claimed in claim 9 in which the diene monomer is present in an amount up to 90% by weight.
12. A method as claimed in claim 5 in which the emulsifying agent is selected from the group consisting of an anionic agent, a cationic agent and a non-ionic agent and is present in an amount within the range of 0.05 to 10% by weight of the monomer or monomers.
13. A method as claimed in claim 5 in which the water soluble diazo initiator is selected from the group consisting of sulfonated azo-nitrile carboxylated azonitrile, an azo-bis-alkylamidinium salt and is present in an amount within the range of 0.01 to 3% by weight of the monomer or monomers.
14. A method as claimed in claim 5 in which the concentration of monomer or monomers in the reaction media is within the range of 1 to 70% by weight.
15. A method as claimed in claim 5 in which the polymerization temperature is within the range of 20°-100° C.
16. Proteins fixed on the latex formed of the polymer particles of claim 1.
US05713056 1975-08-22 1976-08-09 Latex of styrene polymers with terminal amino-sulfonated groups and method of making Expired - Lifetime US4064080A (en)

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CA (1) CA1070875A (en)
DE (1) DE2637603C2 (en)
DK (1) DK151036C (en)
ES (1) ES450892A1 (en)
FR (1) FR2321519B1 (en)
GB (1) GB1511783A (en)
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4226747A (en) * 1977-08-03 1980-10-07 Hoffmann-La Roche Inc. Immunological diagnostic reagents comprising thio-amine terminated latex particles
US4401765A (en) * 1981-09-01 1983-08-30 E. I. Du Pont De Nemours And Company Covalently bonded high refractive index particle reagents and their use in light scattering immunoassays
US4480042A (en) * 1981-10-28 1984-10-30 E. I. Du Pont De Nemours And Company Covalently bonded high refractive index particle reagents and their use in light scattering immunoassays
US4581337A (en) * 1983-07-07 1986-04-08 E. I. Du Pont De Nemours And Company Polyether polyamines as linking agents for particle reagents useful in immunoassays
US4703018A (en) * 1985-02-20 1987-10-27 E. I. Du Pont De Nemours And Company High refractive index haloalkyl-functional shell-core polymers and their use in light scattering immunoassays
EP0318452A1 (en) * 1987-10-29 1989-05-31 Monsanto Europe S.A. Immobilised enzymes and their use in aminoacid electrosensors
US5401636A (en) * 1992-10-21 1995-03-28 E. I. Du Pont De Nemours And Company Enhanced sensitivity agglutination assays multivalent ligands
US5858648A (en) * 1996-11-04 1999-01-12 Sienna Biotech, Inc. Assays using reference microparticles
US5910534A (en) * 1996-07-15 1999-06-08 Bayer Aktiengesellschaft Stable, aqueous dispersions of copolymers based on conjugated, aliphatic dienes and vinyl aromatic compounds
US5981719A (en) * 1993-03-09 1999-11-09 Epic Therapeutics, Inc. Macromolecular microparticles and methods of production and use
US6090925A (en) * 1993-03-09 2000-07-18 Epic Therapeutics, Inc. Macromolecular microparticles and methods of production and use

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63238112A (en) * 1987-03-20 1988-10-04 Ibm Depolymerizable polymer
JPH0490271U (en) * 1990-12-19 1992-08-06

Citations (4)

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Publication number Priority date Publication date Assignee Title
US2376014A (en) * 1941-06-26 1945-05-15 Goodrich Co B F Polymerization of unsaturated organic compounds
US2396997A (en) * 1942-11-11 1946-03-19 Goodrich Co B F Polymerization of unsaturated organic compounds in the presence of sulphur-containing modifiers of polymerization
US2683698A (en) * 1952-11-14 1954-07-13 Dow Chemical Co Stable emulsions of hydrocarbon polymers and method of making the same
US4013824A (en) * 1973-05-16 1977-03-22 Phillips Petroleum Company Mixing of organosulfur molecular weight modifier with emulsifier in presence of monomer or diluent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2376014A (en) * 1941-06-26 1945-05-15 Goodrich Co B F Polymerization of unsaturated organic compounds
US2396997A (en) * 1942-11-11 1946-03-19 Goodrich Co B F Polymerization of unsaturated organic compounds in the presence of sulphur-containing modifiers of polymerization
US2683698A (en) * 1952-11-14 1954-07-13 Dow Chemical Co Stable emulsions of hydrocarbon polymers and method of making the same
US4013824A (en) * 1973-05-16 1977-03-22 Phillips Petroleum Company Mixing of organosulfur molecular weight modifier with emulsifier in presence of monomer or diluent

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Chem. Absts. vol. 71:22520n, Application--Latexes--Emulsion Polymerization, Williams et al. *
Chem. Absts., vol. 75:37533a, Telomers with Terminal Amino Groups, Fokina et al. *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4226747A (en) * 1977-08-03 1980-10-07 Hoffmann-La Roche Inc. Immunological diagnostic reagents comprising thio-amine terminated latex particles
US4401765A (en) * 1981-09-01 1983-08-30 E. I. Du Pont De Nemours And Company Covalently bonded high refractive index particle reagents and their use in light scattering immunoassays
US4480042A (en) * 1981-10-28 1984-10-30 E. I. Du Pont De Nemours And Company Covalently bonded high refractive index particle reagents and their use in light scattering immunoassays
US4581337A (en) * 1983-07-07 1986-04-08 E. I. Du Pont De Nemours And Company Polyether polyamines as linking agents for particle reagents useful in immunoassays
US4703018A (en) * 1985-02-20 1987-10-27 E. I. Du Pont De Nemours And Company High refractive index haloalkyl-functional shell-core polymers and their use in light scattering immunoassays
EP0318452A1 (en) * 1987-10-29 1989-05-31 Monsanto Europe S.A. Immobilised enzymes and their use in aminoacid electrosensors
US4983510A (en) * 1987-10-29 1991-01-08 Monsanto Company Enzymes immobilized on latex polymer particles for use with an amino acid electrosensor
US5401636A (en) * 1992-10-21 1995-03-28 E. I. Du Pont De Nemours And Company Enhanced sensitivity agglutination assays multivalent ligands
US5981719A (en) * 1993-03-09 1999-11-09 Epic Therapeutics, Inc. Macromolecular microparticles and methods of production and use
US6090925A (en) * 1993-03-09 2000-07-18 Epic Therapeutics, Inc. Macromolecular microparticles and methods of production and use
US6268053B1 (en) 1993-03-09 2001-07-31 Epic Therapeutics, Inc. Macromolecular microparticles and methods of production and use
US5910534A (en) * 1996-07-15 1999-06-08 Bayer Aktiengesellschaft Stable, aqueous dispersions of copolymers based on conjugated, aliphatic dienes and vinyl aromatic compounds
US5858648A (en) * 1996-11-04 1999-01-12 Sienna Biotech, Inc. Assays using reference microparticles

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Publication number Publication date Type
NL7609295A (en) 1977-02-24 application
LU75640A1 (en) 1977-04-22 application
DE2637603A1 (en) 1977-03-03 application
CA1070875A (en) 1980-01-29 grant
JPS569161B2 (en) 1981-02-27 grant
GB1511783A (en) 1978-05-24 application
CA1070875A1 (en) grant
FR2321519B1 (en) 1979-02-02 grant
BE845402A (en) 1977-02-21 grant
ES450892A1 (en) 1977-08-16 application
DK151036B (en) 1987-10-12 grant
DK377576A (en) 1977-02-23 application
DE2637603C2 (en) 1984-03-15 grant
FR2321519A1 (en) 1977-03-18 application
JPS5244868A (en) 1977-04-08 application
NL165472C (en) 1981-04-15 grant
DK151036C (en) 1988-03-07 grant
BE845402A1 (en) grant

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